Disazo dyes having a beta-(-p-hydroxyphenyl)-propionic acid or a derivative thereof as the coupling component

ABSTRACT

OR -NH-CO-(CH2)N-CO-NH-   N DENOTIG ZERO OR ONE OF THE INTEGERS 1 TO 6.     1-((4-((4-((2-HO,5-(R-CH2-CH2-)PHENYL)-N=N-)PHENYL)-A-)-   PHENYL)-N=N-),2-HO,5-(R1-CH2-CH2-)BENZENE   WHERE R AND R1 MASY BE IDENTICAL OR LDIFFERENT AND EACH DENOTES A CYANO, CARBOXYL, CARBVALKOXY, UNSUBSTITUTED AMIDE OR SUBSTITUTED AMIDE GROUP AND -A- DENOTES A DIRECT BOND, AND OXYGEN ATOM, A SULFUR ATOM, OR ONE OF THE FOLLOWING BRIDGING GROUPS:   -NH-, -SO2, -CO-, -NH-CO-, -N(-CH3)-CO-, -N(-C2H5)-CO-,   -SO2-NH-, -NH-CO-NH-, -(2-(O=)1,3-IMIDAZOLIDINYLENE)-   -N(-CH3)-CO-N(-CH3)-, -(2-(O=),4-CH3-IMIDAZOLIDIN-1,3-   YLENE)-   -(2-(O=)HEXAHYDROPYRIMIDIN-1,3-YLENE)-,   -N(-CH3)-SO2-N(-CH3)-, CYCLOHEXYLIDENE, -CH2-, -C(-CH3)2- DISAZO DYES HAVING A B-(P-HYDROXPHENYL)-PROPIONIC ACID OR A DERIVATIVE THEREOF AS THE COUPLING COMPONENT; THEY ARE USEFUL FOR DYEING SYNTHEIC POLYAMIDED OR POLYESTERS AS FIBERS AND TEXTILE MATERIALS TO GIVE DYEINGS FAST TO LIGHT AND WET TREATMENTS AND TO HIGH TEMPERATURE, PARTICULARLY THOSE DYES OF THE FORMULA:

United States Patent Claims priority, application Germany, Oct. 19, 1968,

P 18 04 070.5 Int. Cl. C09b 35/14; D06p 1/06 US. Cl. 260-175 4 Claims ABSTRACT OF THE DISCLOSURE Disazo dyes having a fl-(p-hydroxyphenyl)-propionic acid or a derivative thereof as the coupling component; they are useful for dyeing synthetic polyamides or polyesters as fibers and textile materials to give dyeings fast to light and wet treatments and to high temperature, particularly those dyes of the formula:

where R and R may be identical or difierent and each denotes a eyano, carboxyl, carbal-koxy, unsubstituted amide or substituted amide group and --A denotes a direct bond, an oxygen atom, a sulfur atom, or one of the following bridging groups:

n denoting zero or one of the integers 1 to 6.

3,657,218 Patented Apr. 18, 1972 ice Examples of carbalkoxy or substituted amido radicals for R and R are: carbomethoxy, carboethoxy, carbopropoxy, carbobutoxy, N-methylcarbamoyl, N,-N-dimethylcarbamoyl, N-ethylcarbamoyl, N,Ndiethylcarbamoyl, N- butylcarbamoyl, N-( -methoxypropyD-amide or radicals having the formula Preferred radicals R and R are cyano, carboxyl, carbomethoxy, carboethoxy, carbopropoxy, carbobutoxy or carbamoyl.

Preferred groups for A are the radicals having the formula -S, -O,

Where m denotes one of the integers 0 to 6 and R denotes a hydrogen atom or a methyl or ethyl group. Of these groups A, -S, -O,

are preferred.

Examples of industrially preferred dyes having the Formula I are the compounds having the formula:

H2NCOCHZOH2 EJ201120 ONHg OH H? R OOCCHz Ha HzCHzCOOR H HO NGCHz H2 HaCHzCN NC CHiCHi where R denotes an alkyl radical having from one to four carbon atoms or a radical having the formula: -CH CH OCH or -(OCH CH OCH The new dyes are suitable for dyeing cellulose esters or polyesters and polyamides. Very fast dyeings are obtained particularly on polyesters and synthetic polyamides, the fastness to light, wet treatments and high temperature being noteworthy. The material to be dyed is preferably fibers and textile material such as woven, nonwoven and knitted fabric, filaments and threads.

The dye having the Formula I may be prepared for example by reacting tetrazo compounds of diamines having the general Formula II:

with coupling components having the general Formula III:

OH on CHgCHgR GHzCHzR (III) The following are specific examples of aromatic diamines having the Formula II:

Compounds having the general Formula III include derivatives of 13-(4-hydroxyphenyl)-propionic acid which couple in ortho-position to the hydroxyl groups, for example [3 (4' hydroxyphenyl) propionnitrile, [3-(4'- hydroxyphenyl) propionic acid, ,8 (4' hydroxyphenyl)-propionic acid methyl, ethyl, propyl, butyl, isobutyl, methylethylene glycol, and methylethylene diglycol esters, and ,8 (4 hydroxyphenyl) propionamide, -methylamide, -ethylamide, -butylamide, -dimethylamide and -diethylamide.

The compounds having the general Formula II can be tetrazotized in the conventional Way, for example in dilute aqueous hydrochloric or sulfuric acid, with or without the addition of dispersing agents, in organic solvents such as glacial acetic acid, or in mixtures of water and organic solvents.

Coupling of the tetrazonium salts of the aromatic amines having the general Formula II with the coupling components having the general Formula III is advantageously carried out in aqueous alkaline solution with an addition of an acid-binding agent such as sodium hydroxide, sodium carbonate or sodium hydrogen carbonate.

The following examples illustrate the invention.

Unless otherwise stated, the parts and percentages in the following examples are by weight.

EXAMPLE 1 20 parts of 4.4'-diaminodiphenyl ether is stirred in a mixture of 600 parts of ice-water and 50 parts by volume of concentrated hydrochloric acid for one hour at 0 to 5 C. parts by volume of a 23% solution of sodium nitrite is allowed to flow in slowly at the same temperature. Stirring is continued for another two hours and then any excess of nitrous acid present is removed by adding sulfamic acid. The diazo solution is then gradually introduced at 0 to 5 C., while adding 350 parts of ice, to a solution of 37 parts of methyl ;8-(4'-hydroxyphenyl)-propionate, 20 parts of 50% caustic soda solution and 30 parts of sodium carbonate in 600 parts of water. When coupling is over, the dye having the formula:

(RH OH HzCHzC OOCH; HzCH COOCH;

which has formed is suction filtered, washed with water and dried. It is a yellow brown powder which dissolves in dimethylformamide with a yellow color.

parts of polyethylene terephthalate fibers is dyed for sixty minutes at C. in a'pressure apparatus in a liquor containing 2,000 parts of water, 0.8 part of the finely divided dye and 2 parts of the sulfonated adduct 0f 80 moles of ethylene oxide to 1 mole of sperm oil alcohol. A pure yellow dyeing is obtained having excellent thermal resistance and outstanding fastness to light and wet treatments.

Other yellow dyes which give dyeing having similar properties on polyesters and polyamides may be prepared in the same way from the tetrazo components and coupling components in the following table.

Example Tetrazo component having Formula (II) Coupling component having Formula (III) CHzCHzCN I HzCHzCO 0 02H;

' TABLE Cpntinued Example Tetrazo component having Formulu (II) Coupling component having Formula (111) 4 (In l Mixture of equal parts 0! compounds with n=zero, 1 and 2.

zCHzC OOCH:

TABLE C0nt1nued Example Tctrazo component having Formula (II) Coupling component having Formula (III) 13 do 9H JIIzCHzCONIHCHmO CH:

14 CH; O H

ILQ-NH: 0=C

NNflz CHZCILCN 15 Same as above (I)H lHiCHzC O O CH:

16 ..d0 (I)H O H CH C 17 ..do OH CH CH COOII (EHgOHjOONHQ CH CH CN CHgCHgCO 0 CH3 Same as above.

TABLMontinued Example Tetrazo component having Formula (II) Coupling component having Formula. (111) 23 Same as above 0H CHaCH C OOCH:

CHa-N-NH2 cmcmcN 25 Same as above 0H CH2 CH: C ON Hz O H 26 cam-Q-mn CH2 CH: C ON H:

27 (3H3 OH GHzCHaC ONE:

29 Same as above 0H CHzCHzC O O CHa 32 Same as above 0H TABLE Continued Example Tetrazo component having Formula (II) Coupling component having Formula (III) CHzCHaCN EXAMPLE 34 24.2 parts of 4,4'-diaminodiphenylurea is stirred for 15 )-P P A Yellow brown y is several hours with 300 parts by volume of water and 0.3

part of the reaction product of oleylamine with about 12 moles of ethylene oxide at room temperature. 50 parts of concentrated hydrochloric acid and 300 parts of ice are added and at 0 to C. 60 parts by volume of 23% sodium nitrite solution is allowed to flow in slowly. Stirring is continued at the same temperature for another two hours and then any excess of nitrous acid present is removed by adding sulfamic acid. The whole is then filtered and the diazo compound is coupled analogously to the method described in Example 1 to 34 parts of p-(4'-hyformed having the formula:

HZCHZC ONII;

It dissolves in dimethylformamide with a deep yellow color.

100 parts of polyamide cloth is treated for ninety minutes at to C. in a liquor containing 1 part of this dye is finely divided form and 2 parts of sulfonated sperm oil alcohol in 2,000 parts of water to dye it. A pure yellow dyeing is obtained which has very good light and wet fastness properties.

Other yellow dyes having similar properties can be prepared in the same way from the tetrazo components and coupling components in the following table:

Tetrazo component having the Coupling component having the CHnCHiCOOH 13 14 I claim: where X is cyano, carboxyl, carbamoyl or carboalkoxy 1. A disazo dye having the formula: of one to five carbon atoms,

Y is

H HO

or CN HQCHZR HQCHZR I where m is one of the integers from 0 to 6 and R is hywhere R and R may be identical or different and each drogen, methyl or ethyl. is cyano, carboxyl, carbamoyl, carbalkoxy of 2 to 5 car- 3. A dye as claimed in claim 1 which has the formula:

3H0H1o O0R3 6111011200018 bon atoms, N-mono or N,N-di-a1kyl-substituted carbamowher R is alkyl of one to four carbon atoms, yl wherein the alkyl substituents have 1 to 4 carbon atoms,

CO0CH2CH20CH3, --CO(OCH2CH2)2OCH3 or CHCH2OCH3 01' -CONH (CH2) 3OCH3 4. The dye having hte formula:

OH HO N=N NH GO NH@ N=N HzCHzCONHg CHzCHgCONHg and A i5 21 dil'CCt bOIld, oxygen sulfur, References Cited NH-, 02, -N N UNITED STATES PATENTS cm can 1,594,828 8/1926 Geller 260-175 -S02-NH-, NHCO-NH-, NC0l?I-- 2,032,133 2/1936 Krebser 260178 H H H H r 2,273,094 2/1942 Fischer et al. 260175 C Z 2,315,232 3/1943 Thurm et a1. 260-478 P 2,726,238 12/1955 Morschel et al. 260-175 X 4- P H CH3 1 2,777,840 1/1957 Liechti et al. 260--175 1 3,183,225 5/1965 Dreyfuss 260--175 X F 40 3,232,928 2/1966 Baumann et a1 260-175 H H 3,421,829 1/1969 Bennett et a 260-480 X 3,578,654 5/1971 Fayre 260-186 where n denotes one of the integers 0 to 6. I

2. A dye as claimed in claim 1 which has the formula: FLOYD HIGEL Primary Exammer 0 H0 US. 01. X.R.

' @NITED STATES PATENT-OFFICE I CERTIFICATE .OF CORRECTION "'iat antih'o I? .'557,218 o baced g rn" 18 19 ,7 l IiW0r s)-- Gerhard Goad 1 vIt"-is}yoeaz'fifiegllthgxh et'zt'or appears in the above-idntifid patn; ,ja'nd that said 'LetceroPatent-are hereby corroct' ed as shown belowzl';

. oi the formula reading "CH CH Should read CH5 CH3 f h T llnefl 41,' that portion of the formula reading "CH CH should i read" CH2----CH line 41,] that portion of the-formula ;v reading CH ---CH -CH Should read CH '--CH-CH' Column 3, l1ne 4 "oxalic acid-bis ta1minophe'nylamide), .l

S ould read oxalic acid-bis+(4-aminophenylamide), line 45,; "succi-nic acid-bis (k -aminophenylamide), should read.

-"succinic a'ci'd-bis-(4'-aminophenylamide), -'--;.jlin

T'ad-ipiofaid-bis laminophehylamide)," should read fiddpic acme-Q1350; ami nophenylamide),

ih-thetble under-I "'Exarhple Yyafte -r",6"? ahd h'forj, I

opium?! 11', inYthef'l;zlb1e-,. Exami)le 33"; that p rtion; of the] formula} reading 'H" should read C Y v l line] 3 "is" should 'r ead in Columh 13 line 30, claim "oxygen sulfur," should I read i 1-- oxygen, .lsulfur, line 35 those portions of the formu1a i.

. I eading ."CH CH2" shoul r 2- 2 "."5 lines 58 h'ould j-r-e-ad I coiu'mn -l r, in" the references, lino 41, '-'Be'nnett eta. should Efidd -v- Bennett e t a1. 5- line 42, "Fayre" should road 2- Eavrf sig e and Sealedthis 5t -day- .br neegrber' 197g,

I I EA L) 'o 5 Y Attost: I i

g .Eliw tn -pmcimmin. V ROBERT ooflscHALK a v. 'Attosting Officer Commissioner of 'P atnts 

